Iodo methane sulphonic acid and homologues thereof



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Pntented Jan. 26, 1932 untrue srnrns PA ENT? VOFFICE t ABBIGNORS T0WINTHROP CHEHKUAL rono eutrnonrrc ecrn nun nouemenne summon ll'oElli-swing. nppltcetion filed heceniher it, into, Eerlal No. 502,854,and in Germany December 34, 1919.

The present invention relates to iodo meth, ene sulphonic acid and itshomologues end to salts thereof, more wherein R stands tor hydrogen oren ellryl group, end to a process of preparing same.

v the general formula wherein R stands for en ellryl group, with sneutral salt or the sulphurous acid, preterehly in the presence of adiluent being inert to the sterting materials under the conditions ofthe reaction. ltdrantageously the reaction is performed in en aqueoussolution et elevated temperature, tor example, on the u eter hath, Whileemploying a Water soluble selt ot the sulphuric ecid. Suchsalts are, foreremplmthe ammonium-, allraliand. allreline eerth metel salts of thesulphurous ncid, hut elso salts oil the sulphurous acid "with orgenichoses containing nitrogen, for erample, methylnmine-, diethylamine, ethylenediamine, piperidine and piperazine sulphites me he used. WhenWorking in the shore in icated menner, firstly n salt or" the iodomethane sulphonic acid or of a homologue thereo't is produced, the kindof suit hein dependent on the hind of salt-0t the sulp urous ecid usedes reacting component The tree iodo methane sulphonic ncid itselt muy heproduced, for example, by digesting its sodium selt "With stronghydrochloric ecid end seperating the precipitated sodium chloride in thecustomary manner. Thus the "tree iodo methane snlphonic sold is ohteinedus a sirupy liquid eesily soluble in Writer end organic solvents, forexample, alcohol end ecetone. Oil course, the iodo methone sulphonicocid or its homologues can 7 perticnlarly to compounds having in form oithe treev acidsthe probable formulaesis-- -methane sulphonic acid.

The salts of the iodo methane sulphonic ecid and its'homologues are forthe greatest part soluble in water depending on the kind of the saltforming base used. The iodo methane sul honic acid, its homologues andsalts thereo' may be used as intermediate products in chemical reactionsThe water to soluble salts have provedes cially valuable es contrastmedia in the tee nique of X-ray pictures for ren :lering visible hollowbodies, especially the hollow organs of warm-hlood- 7 ed organisms, suchas bloodsvessels, articular t5 cavities, fistulee, urinary passages, thepelves of the kidneys, and the like. i For example, in order to renderthe urinary passages visible the iodo methane sulphonic acid salt or asolution thereof can he introduced into the orno ganism by one of thecustomary methods, and an -ray photograph taken at or during the timethe iodo methane sulphonic acid salt is excreted With the urine. I

it may he mentioned that the iodo methane es sulphonic acid and itshomologues also have proved ooteinable by reacting u on another halogenmethane sulphonic acid, or instance, chloroor bronco-methane sulphonicacid with e salt of hydro iodic acid, preferably an alkali or alkalineearth metal salt thereof.

The following examples illustrate the invention Withoutrestrioting itthereto Ema/mp2s 1.-5l),4l parts by Weight of crystallized sodiumsulphite are dissolved in see a parts by Weight of Water and thesolution is strongly stirred With 54 parts by weight of methylene iodidefor 8 hours at 70 6G. The solution containing the sodium iodo methenesulphonate formed is evaporated to dryness. ltd

The sodium iodide formed is extracted by means of acetone and theremaining residue of sodium iodo methane sul honate is recrystallizedfrom methyl alco ol. Thus well develo d crystals of pure sodium iodomethane sulp onate in a yield of up to 95% of the theory are obtained.They decompose on heatingin the dry state with liberation of iodinewithout melting in a characteristic manner. They dissolve in water witha neutral reaction and are soluble for example also in methyl alcoholand in dilute ethyl alcohol, but insolublein ether, acetone, chloroformand petroleum ether.. On treatment with nitrite in acid solution noiodine is liberated. From a concentrated aqueous solution of sodium iodomethane sulphonate the calcium salt can be salted out by means ofcalcium'chloride.

' The free acid can be obtained, for example from the sodium salt b theaddition strong hydrochloric aci 'It is a liquid, syrupy at roomtemperature, miscible in all pro ortions with water and alcohol.

sample 2-54 ams of meth lene iodide are shaken for 12 ours at 75 with42,5 grams of crystallized magnesium sulphite in 200 ccs. 0 water andccs.-of alcohol. After the separation of a little unchanged methyleneiodide the solution is evaporated to drynes and the residue crystallizedfrom a mixture of methyl alcohol and ether. There are obtained colorlesscrystals of the mag ncsium salt of iodo methane sulphonic acid which arevery readily soluble in water and 0 similar properties to the sodiumsalt already described.

EamnpZe3.-When in Exam le 1 the sodium sulphite is replaced by t equantity of monomethylamine sul ite, obtain'able by passing sulphurdioxi e into an aqueous solution of monomethylamine and the process iscarried out in a manner analogous to that described in Example 1, themonomethylamine salt of iodo methane sulphonic and is obtained incolorless water soluble crystals, which melt at E i-745 C. The sameproduct is obtained, for example,

by digesting parts by weight of sodium iodo methane sulphonate for ashort time with 100 parts by weight of concentrated hydrochloric acid,filtering from the separated sodium chloride, evaporating the excesshy-. drochloric acid completely at 100 C. and after dissolving in waterthe iodo methane sulphonic acid (which remains as a syrup), neutralizingwith aqueous methylamine solution. The solution is evaporated untilcrystallization occurs and the separation is completed by the additionof a mixture of methyl alcohol and ether. After separation and dryingthe methylamine salt of iodo methane sulphonic acid is obtainedas abovein colorless crystals, which are readily soluble in water with a neutralreaction. The iodo methane uivalent sul honic acid can likewise beneutralized wit other organic and inorganic bases instead of withmethylamine and the corresponding salts obtained in an analogous manner.

The salts of iodo methane sulphonic acid with other, for example,organic bases, such as dimethylamine, can also be obtained by causingthe calcium iodo methane sulphonate, obtainable in accordance with Examle 1, to act on an equimolecular quantity of dlmethylamine sulphate inalcoho 'c agueous solution,

separating from preci 1 calcium sulphate, evaporatin to ryness andworking up as in' Examp e 1.. Colorless crystals, readily soluble inwater with a neutral reaction are thus obtained.

' Example 4.197,4 parts b weight of ethylidene iodide in 360 arts yweight of water are shaken at 95 for 48 hours in a closed vessel with176,4 parts b neutral sodium sul'phite. The uid after separation from asmall uanti of 1m? changed'eth lidene iodide gsevaPorated to dryness ata ow temperatures The salt mixture remaining is extracted with acetoneand the portion insoluble therein is'crystallized from 3-4 parts ofmethyl alcohol. The sodium salt of al ha-iodoethane-al ha-sulphonic acidcrysta lizes in colorless ustrous leaflets, which dissolve readily inwater with a neutral reaction. y

We claim 1. As new products the compounds having in form of the acidsthe probable formula wherein R stands "for hydrogen or an alkyl group,said products being n form of the.

acids sirupy li uids easily soluble in water and organic so vents, beingvaluable intermediate products, being in form of their water solublesalts valuable contrast media for X-ray photography.

2. As a new roduct the compound having in form of its acid the formula HCI- SO,H, said acid being a sirupy liquid easily soluble in water andorganic solvents, being a valu- "weight I of grodpp, with e neutral saltof the sulphurons eel h. The process which comprises heating a compoundof the probable formula R--CHI wherein R- stands for hydrogen or analkyl 7 group with a neutral salt of the sulphurous acid in the presenceof a. diluent inert to the starting materials.

h. The process which comprises heating a compound of the probableformulae- R-CHL l5 wherein R stands for hydrogen or an alkyl group, witha water soluble neutral salt of the snlphurons acid in the presence ofwater.

i. The process which comprises heating methylene iodide with e watersoluble neulw trel salt of the sulphnrons acid in the presence o'lwater.

8. The process which comprises heating methylene iodide with on alkalimetal salt ol the snlphurons acid in the presence of W water. v

9. The process which comprises heating methylene iodide with an alkalimetal salt of the sulphur-oils acid in the resence of water withstirring to about 7W B0 lit. The process which comprisesheating 50 partsby weight of sodium sulphite, 200 parts loy weight of water and '54parts by weight of methylene iodide at 10 U. during a period of 8 hourswith strongly stirring,

$5 evaporating the reaction mixture to dryness,

removing the sodium iodide formed by extraction with acetone andrecrystallizing the residue obtained from methylalcohol.

in testimony whereol, we ofix our signei ANTUN @SSENBECKL ERNST TIE'lZE.GERHARD HECHT.

